CN113651311A - Alkynyl carbon material, preparation method thereof and composite electrode - Google Patents
Alkynyl carbon material, preparation method thereof and composite electrode Download PDFInfo
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- CN113651311A CN113651311A CN202110808975.7A CN202110808975A CN113651311A CN 113651311 A CN113651311 A CN 113651311A CN 202110808975 A CN202110808975 A CN 202110808975A CN 113651311 A CN113651311 A CN 113651311A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 80
- 125000000304 alkynyl group Chemical group 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 41
- 239000005997 Calcium carbide Substances 0.000 claims abstract description 26
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011324 bead Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 36
- -1 alkynyl carbon Chemical compound 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 239000011593 sulfur Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 9
- 238000003801 milling Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- QNMKKFHJKJJOMZ-UHFFFAOYSA-N hexaiodobenzene Chemical compound IC1=C(I)C(I)=C(I)C(I)=C1I QNMKKFHJKJJOMZ-UHFFFAOYSA-N 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000011148 porous material Substances 0.000 abstract description 14
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010399 three-hybrid screening Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides an alkynyl carbon material, a preparation method thereof and a composite electrode, comprising the following steps: mixing calcium carbide and hexahalobenzene with ball-milling beads, wherein the mass ratio of the ball-milling beads to the total mass of the calcium carbide and the hexahalobenzene is (10-150): 1, ball-milling for 24-48 h at the speed of 400-1000 r/min to obtain mixed powder; the high-purity alkynyl carbon material is obtained through post-treatment, and has high purity and yield, good conductivity, nano-scale pores and interlamellar spacing suitable for metal ion conduction, and is beneficial to lithium ion transmission and buffering of volume strain in the electrochemical reaction process.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to an alkynyl carbon material, a preparation method thereof and a composite electrode.
Background
As one of the most potential next-generation secondary batteries, the lithium-sulfur battery has the advantages of high theoretical specific capacity of 1675mAh/g, high energy density of 2600Wh/kg, environmental friendliness, rich sulfur storage and the like, and is widely researched. However, the electronic insulation property (10-30S/cm) of elemental sulfur and the volume strain during discharge, the sulfur anode is usually required to be compounded with a conductive matrix material, and the carbon material is considered as the first carrier of the compound. The alkynyl carbon material represented by the graphyne has unique nano-scale pores, a two-dimensional layered conjugated framework structure and semiconductor properties, and the two-dimensional plane spacing of the alkynyl carbon material is larger than that of graphene, so that the alkynyl carbon material is favorable for the rapid transmission of lithium ions in the gaps. However, most of the prior art prepares the alkynyl carbon material by cross-coupling reaction of hexaalkynyl benzene, the reaction process is complex, the coupling efficiency is low, the reaction system can generate more byproducts, and bulk polymerization of monomers can occur, so that the synthesis cost of the alkynyl carbon material is greatly increased, and the yield and the purity of the synthesized alkynyl carbon are low.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the alkynyl carbon material, the preparation method thereof and the composite electrode.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of an alkynyl carbon material comprises the following steps:
s1, mixing calcium carbide and hexahalobenzene with ball milling beads, wherein the mass ratio of the ball milling beads to the total mass of the calcium carbide and the hexahalobenzene is (10-150): 1, ball-milling for 24-48 h at the speed of 400-1000 r/min to obtain mixed powder;
s2, sieving the mixed powder, and performing post-treatment to obtain the alkynyl carbon material.
Further, in step S1, the molar ratio of the calcium carbide to the hexahalobenzene is (2-20): 1.
further, in step S1, after vacuum drying the calcium carbide, the hexahalobenzene, the ball milling beads and the ball milling tank, ball milling is performed in a glove box filled with argon atmosphere protection, the ball milling beads have diameters of 5mm, 8mm, 10mm, 12mm and 15mm, and the ball milling bead ratios of different diameters are q: m: n: o: and p, wherein the values of q, m, n, o and p are 1-5.
Further, in step S1, a planetary ball mill is used for ball milling, and the ball milling beads are alumina ceramic milling balls, stainless steel milling balls or zirconia milling balls.
Further, in step S2, the sieving is performed by a sieve of 140 to 300 meshes.
Further, in step S2, the post-treatment is washing and then calcining or washing after calcining, and the washing is performed with 0.1 to 0.5mol/L of dilute nitric acid solution; the calcination is carried out at 300-500 ℃ for 2-5 h under the nitrogen atmosphere, and the temperature rise speed is 2-5 ℃/min.
Further, in step S1, the hexahalobenzene is at least one of hexabromobenzene, hexachlorobenzene and hexaiodobenzene.
The invention also provides an alkynyl carbon material prepared by the preparation method.
The alkynyl carbon/sulfur composite electrode is prepared by mixing and thermally treating the alkynyl carbon material and elemental sulfur to obtain an alkynyl carbon/sulfur composite material, mixing, coating and cutting the alkynyl carbon/sulfur composite material to obtain the alkynyl carbon/sulfur composite electrode, and the alkynyl carbon/sulfur composite electrode is used for preparing a lithium-sulfur battery.
Further, the mass ratio of the alkynyl carbon material to the elemental sulfur is 3: 7, and the heat treatment is carried out at 158 ℃ for 10 h.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides a preparation method of an alkynyl carbon material, which is characterized in that the alkynyl carbon material is synthesized by a mechanical ball milling method, mechanical energy generated by mechanical ball milling and heat-induced calcium carbide and hexahalobenzene are subjected to multiphase chemical reaction, and the high-purity alkynyl carbon material is obtained by post-treatment, and has the advantages of mild operation conditions, low cost, simple and convenient process, energy conservation, environmental protection, strong independence and easy batch production;
compared with other ball milling methods for preparing carbon materials, the preparation method provided by the invention has the advantages that the purity and yield of the prepared alkynyl carbon material are high, the carbon content is up to 64%, the yield is up to 72%, the prepared alkynyl carbon material has good conductivity, nano-pores and interlayer spacing suitable for metal ion conduction, and the preparation method is beneficial to lithium ion transmission and buffers volume strain in the electrochemical reaction process;
furthermore, the post-treatment promotes the ball-milling reaction product to further react completely through calcination, improves the yield of the alkynyl carbon material, removes redundant impurities through further acid washing, improves the purity of the alkynyl carbon product,
the composite electrode prepared by the alkynyl carbon material synthesized by the invention is used for a lithium-sulfur battery, the high-efficiency utilization of active sites is realized, the electrochemical activity and the cycle life of the battery are greatly improved, the first discharge specific capacity is 588mAh/g, the first discharge specific capacity is still maintained at 420mAh/g after 100-week cycle, and the stable electrochemical energy storage can be realized.
Drawings
FIG. 1 is an X-ray diffraction spectrum of an alkynyl carbon material provided in example 1 of the present invention and comparative examples 1 to 2;
FIG. 2 is a scanning electron micrograph of the alkynyl carbon material provided in example 2 at different magnifications;
FIG. 3 shows an X-ray photoelectron spectroscopy full scan XPS spectrum and C spectrum of the alkynyl carbon material provided in example 31sXPS spectra;
FIG. 4 is a constant current charge-discharge curve of the alkynyl carbon/sulfur composite electrode material provided in example 4;
FIG. 5 is a current-voltage curve of the alkynyl carbon/sulfur composite electrode material provided in example 4;
Detailed Description
The invention will be further described with reference to the drawings and the detailed description, but the invention is not limited thereto.
The technical scheme adopted by the invention for realizing the purpose is as follows:
step 1: after calcium carbide, hexahalobenzene, ball-milling beads and a ball-milling tank are dried in vacuum, mixing the raw materials in a glove box filled with argon atmosphere for protection according to a certain proportion, and packaging the ball-milling tank; wherein the molar ratio of calcium carbide to hexahalobenzene is (2-20): 1, the mass ratio of the ball milling beads to the total mass of the calcium carbide and the hexahalobenzene is (10-150): 1; the total mass of the ball milling beads is 750g, the diameters of the ball milling beads are 5mm, 8mm, 10mm, 12mm and 15mm, and the proportion of the ball milling beads with different diameters is q: m: n: o: p, wherein the values of q, m, n, o and p are 1-5;
step 2: ball-milling for 24-48 h at the speed of 400-1000 r/min by adopting a planetary ball mill to obtain mixed powder;
and step 3: after the mixed powder is sieved by a sieve of 140-300 meshes, post-treatment is carried out, and drying is carried out, so that the alkynyl carbon material is obtained;
preferably, in step 1, the hexahalobenzene is at least one of hexabromobenzene, hexachlorobenzene and hexaiodobenzene.
Preferably, in step 1, the ball milling beads may be alumina ceramic milling beads, stainless steel milling beads or zirconia milling beads.
Preferably, in step 3, the post-treatment is washing and then calcining or calcining and then washing;
preferably, the washing is to wash the sample for a few times by using 0.1-0.5 mol/L dilute nitric acid solution until the eluate is neutral, and then to carry out suction filtration and drying;
preferably, the calcination is to weigh a certain amount of sample, place the sample in a porcelain boat, calcine the sample in a tube furnace protected by nitrogen atmosphere, heat the sample to 300-500 ℃ at a heating rate of 2-5 ℃/min, keep the temperature for 2-5 h, and naturally cool the sample to room temperature.
The alkynyl carbon material is a novel two-dimensional carbon material in recent years, has the advantages of fast electron transmission, layered porosity, rich ion channels and the like, is a proper sulfur-carrying matrix, and is favorable for obtaining a high-performance lithium sulfur battery when being used for the lithium sulfur battery.
The alkynyl carbon material prepared by the invention has good conductivity and the capacity of buffering the volume strain of an electrode, and a high-performance composite electrode can be prepared by compounding the alkynyl carbon material prepared by the invention and elemental sulfur, and the composite electrode is used for preparing a lithium-sulfur battery, and the specific operation is as follows:
and (3) mixing the following components in percentage by mass: 7, uniformly mixing the alkynyl carbon material and elemental sulfur, placing the mixture in a high-pressure reaction kettle for heat treatment at 158 ℃ for 10 hours to obtain an alkynyl carbon/sulfur composite material, mixing, coating and cutting the mixture to obtain an alkynyl carbon/sulfur composite electrode, assembling the alkynyl carbon/sulfur composite electrode into a button lithium-sulfur battery, and testing the electrochemical performance of the button lithium-sulfur battery.
Example 1
1) The molar ratio of the calcium carbide and the hexabromobenzene after vacuum drying is 5: 1, and the mass ratio of the stainless steel grinding ball to the total mass of the calcium carbide and the hexabromobenzene is 10: 1, grinding balls (5mm, 8mm, 10mm, 12mm, 15mm) with different diameters in proportion of 5: 4: 3: 2: 1, mixing and packaging a ball milling tank in a glove box filled with argon atmosphere for protection;
2) ball-milling for 24 hours at the speed of 1000r/min by adopting a planetary ball mill, and sieving by using a 140-mesh sieve to obtain a mixed product;
3) and washing the screened sample for a few times by using 0.5mol/L dilute nitric acid solution until the eluate is neutral, carrying out suction filtration and drying, weighing 3g of the sample, placing the weighed sample in a porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 5 hours, carrying out calcination treatment, and naturally cooling to room temperature to obtain the alkynyl carbon material.
Example 2
The proportion of grinding balls (5, 8, 10, 12, 15mm) with different diameters is 2: 1: 3: 5: 4, the rest is the same as example 1.
Example 3
The proportion of grinding balls (5, 8, 10, 12 and 15mm) with different diameters is 1: 3: 5: 2: 4, the rest is the same as example 1.
Example 4
1) Vacuum dried calcium carbide and hexahalobenzene (mixture of hexabromobenzene, hexachlorobenzene and hexaiodobenzene) in a molar ratio of 10: 1, the mass ratio of the alumina ceramic grinding ball to the total mass of the calcium carbide and the hexahalobenzene is 100: 1, grinding ball (5, 8, 10, 12, 15mm) ratio of different diameters 3: 4: 2: 2: 1, mixing and packaging a ball milling tank in a glove box filled with argon atmosphere for protection;
2) ball-milling for 48h at the speed of 500r/min by adopting a planetary ball mill, and screening the obtained ball-milled sample by using a 200-mesh screen;
3) weighing 3g of screened sample, putting the screened sample in a porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 450 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 2h, calcining, naturally cooling to room temperature, washing the calcined sample with 0.3mol/L dilute nitric acid solution for a few times until the eluate is neutral, and then carrying out suction filtration and drying to obtain the alkynyl carbon material.
Example 5
1) The vacuum dried calcium carbide and hexahalobenzene (mixture of hexabromobenzene and hexaiodobenzene) were mixed at a molar ratio of 20: 1, the mass ratio of the zirconium oxide grinding beads to the total mass of the calcium carbide and the hexahalobenzene is 60: 1, grinding ball (5, 8, 10, 12, 15mm) ratio of different diameters 4: 3: 2: 5: 1, mixing and packaging a ball milling tank in a glove box filled with argon atmosphere for protection;
2) ball-milling for 36h at the speed of 800r/min by adopting a planetary ball mill, and screening the obtained ball-milled sample by using a 300-mesh sieve;
3) and washing the screened sample for a few times by using 0.2mol/L dilute nitric acid solution until the eluate is neutral, carrying out suction filtration and drying, weighing 3g of the sample, placing the weighed sample in a porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 450 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3h, carrying out calcination treatment, and naturally cooling to room temperature to obtain the alkynyl carbon material.
Example 6
1) The molar ratio of the calcium carbide and the hexabromobenzene after vacuum drying is 2: 1, and the mass ratio of the stainless steel grinding balls to the total mass of the calcium carbide and the hexaiodobenzene is 150: 1, grinding balls (5mm, 8mm, 10mm, 12mm, 15mm) with different diameters in proportion of 5: 2: 1: 4: 3, mixing and packaging the mixture in a glove box filled with argon atmosphere for protection;
2) ball-milling for 24 hours at the speed of 400r/min by adopting a planetary ball mill, and sieving by a 250-mesh sieve to obtain a mixed product;
3) and washing the screened sample for a few times by using 0.1mol/L dilute nitric acid solution until the eluate is neutral, carrying out suction filtration and drying, weighing 3g of the sample, placing the weighed sample in a porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 500 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, carrying out calcination treatment, and naturally cooling to room temperature to obtain the alkynyl carbon material.
Example 7
1) The molar ratio of the calcium carbide and the hexachlorobenzene after vacuum drying is 10: 1, the mass ratio of the alumina ceramic grinding ball to the total mass of the calcium carbide and the hexahalobenzene is 100: 1, grinding ball (5, 8, 10, 12, 15mm) ratio of different diameters 3: 5: 4: 1: 2, mixing and packaging the materials in a glove box filled with argon atmosphere for protection;
2) ball-milling for 48h at the speed of 600r/min by adopting a planetary ball mill, and screening the obtained ball-milled sample by using a 200-mesh sieve;
3) weighing 3g of screened sample, heating to 350 ℃ at a heating rate of 3 ℃/min in a tubular furnace protected by nitrogen atmosphere in a porcelain boat, keeping the temperature for 4h for calcination, naturally cooling to room temperature, washing the calcined sample with 0.3mol/L dilute nitric acid solution for a few times until the eluate is neutral, carrying out suction filtration and drying to obtain the alkynyl carbon material.
Example 8
1) The vacuum dried calcium carbide and hexahalobenzene (mixture of hexabromobenzene and hexaiodobenzene) were mixed at a molar ratio of 20: 1, the mass ratio of the zirconium oxide grinding beads to the total mass of the calcium carbide and the hexahalobenzene is 60: 1, grinding ball (5, 8, 10, 12, 15mm) with different diameters in proportion of 1: 4: 2: 3: 5, mixing and packaging the mixture in a glove box filled with argon atmosphere for protection;
2) ball-milling for 36h at the speed of 800r/min by adopting a planetary ball mill, and screening the obtained ball-milled sample by using a 300-mesh sieve;
3) and washing the screened sample for a few times by using 0.2mol/L dilute nitric acid solution until the eluate is neutral, carrying out suction filtration and drying, weighing 3g of the sample, placing the weighed sample in a porcelain boat in a tubular furnace protected by nitrogen atmosphere, heating to 450 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3h, carrying out calcination treatment, and naturally cooling to room temperature to obtain the alkynyl carbon material.
Comparative example 1
The only difference from example 1 is that the ball-milled screened samples were only acid washed.
Comparative example 2
The only difference from example 1 is that the ball milled screened samples were only calcined.
Preparing an electrode and assembling a battery: weighing 0.6g of alkynyl carbon material obtained in the embodiment 4, uniformly mixing the alkynyl carbon material with 1.4g of elemental sulfur, placing the mixture in a high-pressure reaction kettle for heat treatment at 158 ℃ for 10 hours to obtain an alkynyl carbon/sulfur composite material, mixing, coating and cutting the mixture to obtain an alkynyl carbon/sulfur composite electrode, taking the provided alkynyl carbon/sulfur composite material as a positive electrode, a lithium sheet as a negative electrode, a polypropylene diaphragm (Celgard2300) as a diaphragm, and 1mol/LLITFSI/DOL (1, 3-dioxolane) + DME (ethylene glycol dimethyl ether) [ 1.0% LiNO3]And (3) assembling a button lithium-sulfur battery as an electrolyte, and testing the electrochemical performance of the button lithium-sulfur battery.
Performance testing
Characterization analysis and performance tests were performed on the alkynyl carbon materials provided in examples 1-8 and comparative examples 1-2:
(1) x-ray diffraction spectroscopic analysis: and qualitatively analyzing the microstructure of the sample by using an XRD-6100X-ray diffractometer, and continuously scanning within the range of 10-80 degrees by using CuK alpha, tube voltage of 40kV and tube current of 30 mA.
(2) Elemental analysis test: the obtained alkynyl carbon was subjected to an elemental analysis test using a Vario Micro cube type elemental analyzer manufactured by Mettler-Torledo instruments.
(3) Scanning electron microscopy test: the morphology of the material was observed using a model JSM-6700F scanning electron microscope, Calzeiss GmbH, Germany, at an accelerating voltage of 20 kV.
(4) X-ray photoelectron spectroscopy: the surface chemistry of the samples was characterized using an AXIS-ULTRAX ray photoelectron spectrometer and the data was fitted using XPS-Peak41 software.
(5) Specific surface area and pore size analysis: the pore volume, the pore size and the distribution of the porous carbon and the specific surface area are tested by adopting a JW-BK122W type specific surface and pore size analyzer of Beijing exquisite-micro-high-Bokojic technology, and nitrogen is used as adsorption gas, and the specific surface area and the pore size distribution of the alkynyl carbon material are obtained by calculation through a BJH method.
(6) And (3) electrochemical performance testing: testing the electrochemical performance of the composite electrode prepared from the alkynyl carbon material by using a Xinwei battery tester, and testing at a voltage of 1.5-3V and a multiplying power of 0.1C (1C: 1675 mAh/g); and performing a current-voltage curve test by using a Chenghua CHI660E electrochemical workstation, wherein the voltage range is 1.5-3.0V, and the scanning speed is 0.1 mV/s.
Characterization analysis and performance testing were as follows:
(1) FIG. 1 is an X-ray diffraction spectrogram of the alkynyl carbon material provided in example 1 and comparative examples 1-2, which shows that, similar to the X-ray diffraction spectrogram of the alkynyl carbon material subjected to the treatment of washing and calcining in the invention, obvious diffraction characteristic peaks appear around 2 theta 21 degrees, 36 degrees and 44 degrees, but the diffraction characteristic peaks of the alkynyl carbon material subjected to the treatment of washing and calcining in the first place are stronger and have fewer impurities, which indicates that the alkynyl carbon material obtained by the treatment manner of washing and calcining in the second place has higher purity, and the alkynyl carbon material obtained in example 1 is subjected to element analysis and test, and the result shows that the carbon content of the obtained alkynyl carbon material is 64%, and the yield of the alkynyl carbon material prepared by the process is up to 72%, the purity and the yield of the alkynyl carbon material prepared by the method are higher than those of the alkynyl carbon material prepared by the existing method.
(2) Fig. 2 is a scanning electron micrograph of the alkynyl carbon material provided in example 2 at different magnifications (10k and 100k), and it can be seen from the micrograph that, due to the non-substrate preparation, a sample with a two-dimensional lamellar structure is agglomerated and curled, irregular nanoparticles are formed, and the material belongs to a typical structure of the alkynyl carbon material, and the surface of the provided alkynyl carbon material is rough, and when the material is used as a positive electrode composite material of a lithium sulfur battery, the material is beneficial to increasing the loading of elemental sulfur and the binding effect on polysulfide.
(3) FIG. 3 shows an X-ray photoelectron spectroscopy full scan XPS spectrum and C spectrum of the alkynyl carbon material obtained in example 31sXPS spectrogram, X-ray photoelectron spectrum peak-splitting fitting junction in the figureAs a result, the obtained alkynyl carbon material has sp, sp2And sp3Three hybrid states, which have the obvious characteristics of alkynyl carbon materials.
(4) Specific surface area and pore size analysis of the alkynyl carbon materials provided in examples 1-8 and comparative examples 1-2, and the test results are shown in Table 1, it can be seen that the alkynyl carbon materials provided in examples 1-8 all have specific surface areas higher than 200m2Has a large pore volume to facilitate sulfur holding, while the alkynyl carbon material in comparative example 1 has a specific surface area of only 25.2m2In conclusion, the alkynyl carbon material provided by the invention has higher specific surface area and pore volume, is beneficial to the loading of active substance sulfur, provides a reaction active site, improves the electrochemical reaction activity, and can inhibit the shuttle effect by physically adsorbing polysulfide.
TABLE 1 data table of specific surface area and pore size analysis of alkynyl carbon materials of example 1 and comparative example
| Sample (I) | Specific surface area (m)2/g) | Pore volume (cm)3/g) | Average pore diameter (nm) |
| Example 1 | 302.4 | 0.300 | 3.90 |
| Example 2 | 228.6 | 0.238 | 7.96 |
| Example 3 | 237.5 | 0.394 | 8.91 |
| Example 4 | 284.8 | 0.410 | 9.07 |
| Example 5 | 289.6 | 0.217 | 11.25 |
| Example 6 | 279.6 | 0.289 | 10.42 |
| Example 7 | 264.23 | 0.256 | 9.45 |
| Example 8 | 246.79 | 0.331 | 4.88 |
| Comparative example 1 | 25.2 | 0.074 | 10.6 |
| Comparative example 2 | 27.5 | 0.097 | 12.5 |
(5) Fig. 4 is a constant current charge-discharge curve of the composite sulfur electrode material prepared from the alkynyl carbon material provided in example 4, in which performance, it can be seen that the alkynyl carbon material/sulfur composite electrode has an obvious charge-discharge platform, which corresponds to an electrochemical reaction in a lithium-sulfur battery cycle process, in addition, a current-voltage curve diagram (fig. 5) of the alkynyl carbon/sulfur composite electrode has high overlap ratio and small peak displacement, which fully proves that the provided alkynyl carbon/sulfur composite electrode has good electrochemical performance and cycle performance, and the provided alkynyl carbon material is an excellent matrix material of the lithium-sulfur battery, thereby providing a new idea for energy storage of the lithium-sulfur battery.
The applicant states that the alkynyl carbon material, the preparation method and the application thereof are illustrated by the above examples, but any modification of the present invention, equivalent replacement of the raw materials selected for the present invention, addition of auxiliary components, and selection of specific modes are within the protection scope and the disclosure scope of the present invention, which should be clear to those skilled in the art of the present invention.
Claims (10)
1. A preparation method of an alkynyl carbon material is characterized by comprising the following steps:
s1, mixing calcium carbide and hexahalobenzene with ball milling beads, wherein the mass ratio of the ball milling beads to the total mass of the calcium carbide and the hexahalobenzene is (10-150): 1, ball-milling for 24-48 h at the speed of 400-1000 r/min to obtain mixed powder;
s2, sieving the mixed powder, and performing post-treatment to obtain the alkynyl carbon material.
2. The method for producing an alkynyl carbon material according to claim 1, wherein in step S1, the molar ratio of calcium carbide to hexahalobenzene is (2-20): 1.
3. the method for preparing an alkynyl carbon material as claimed in claim 1, wherein in step S1, the calcium carbide, the hexahalobenzene, the ball-milled beads and the ball-milling pot are vacuum-dried and then ball-milled in a glove box filled with argon atmosphere protection, the ball-milled beads have diameters of 5mm, 8mm, 10mm, 12mm and 15mm, and the ball-milled beads with different diameters have a ratio of q: m: n: o: and p, wherein the values of q, m, n, o and p are 1-5.
4. The method for preparing an alkynyl carbon material as claimed in claim 1, wherein in step S1, ball milling is performed by using a planetary ball mill, and the ball milling beads are alumina ceramic milling balls, stainless steel milling balls or zirconia milling balls.
5. The method for producing an alkynyl carbon material according to claim 1, wherein in step S2, the sieving is performed with a 140-300 mesh sieve.
6. The method for preparing an alkynyl carbon material as claimed in claim 1, wherein in step S2, the post-treatment is washing and then calcining or calcining and then washing, and the washing is performed with 0.1-0.5 mol/L dilute nitric acid solution; the calcination is carried out at 300-500 ℃ for 2-5 h under the nitrogen atmosphere, and the temperature rise speed is 2-5 ℃/min.
7. The method for producing an alkynyl carbon material according to claim 1, wherein in step S1, the hexahalobenzene is at least one of hexabromobenzene, hexachlorobenzene and hexaiodobenzene.
8. An alkynyl carbon material produced by the production method according to any one of claims 1 to 7.
9. The alkynyl carbon/sulfur composite electrode is characterized in that the alkynyl carbon material and elemental sulfur in claim 8 are mixed and subjected to heat treatment to obtain an alkynyl carbon/sulfur composite material, the alkynyl carbon/sulfur composite material is subjected to mixing, coating and cutting to obtain the alkynyl carbon/sulfur composite electrode, and the alkynyl carbon/sulfur composite electrode is used for preparing a lithium-sulfur battery.
10. The alkynyl carbon/sulfur composite electrode according to claim 9, wherein the mass ratio of alkynyl carbon material to elemental sulfur is 3: 7, and the heat treatment is carried out at 158 ℃ for 10 h.
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